Halogenated condensation products



Patented Jan. 27, 1948 TATE assume OGENATED COENSATION PRODUCTfi JosephB. Niedcrl, Brooklyn, N. Y.

No Bra. Application April 19, 1915,

. Serial No. 589.281 7 This invention relates to condensation productsof poly-halogenated carbonyl compounds with long-chain substitutedphenols, such condensation products being insecticides and fungicides.

as well as bactericides. This combination of highly desirable propertieis obtained by condensing poly-halogenated carbonyl compounds withphenols possessing initially high phenol coeilicients.

More particularly, this invention relates to the condensation productsof poly-halogenated carbonyl compounds possessing at least onetrihaloaceto group (CXaCO) with phenol having a tt-octyl group((CHa)3CCH2C(CH3)2-;amp ,1!- tetramethyl-butyl, or diisobutyl group) asthe side chain or as one of the side chains (J. B. Niederl et al.,Journ. Am. Chem. 800., vol. 55, p. 2571 (1933)), such phenols beingknown to possess phenol coefllcients of about 150 (JI B. Niederl, Ind.Eng, Chem., vol. 30. p. 1273 (1938)).

In general the chemical nature of the condensation products embodied inthis invention may be expressed by the formula given below:

etc.. while Z designates hydrogen, halogen, a nitro group. a carboxylgroup, a short chain alkyl radical such as: methyl, ethyl, etc.. an arylradical such as phenyl, an aralkyl radical such as benzyl, a cyclo-alkylradical such as oyclohexyl,

Y OH i Z Z-nitro-i-tt-octylphenol: phenol; 8-methyl-4-tt-octylpheno1;4-methyl-2- The tt-octylphenols utilized in this invention comprisespecifically the following compounds:

2-chloro 4-tt-octylphenol; 2- 2-iodo-4-tt-octy1phep-tt-octylphenol;bromo--tt-octylphenol;

n01; 2.6-dichloro-e-tt-octylphenol; 2-6-dibromo-2,6-di-iodo-4-tt-octylphenol;

2-methyl-4-tt-octyle-tt-octylphenol;

tt-octylphenol; 2-chloro-5-methyl-4-tt-cctylphenol;2-bromo-fi-methyl-e-tt-octylphenol; 2-iodo- 5-methyl-4-tt-octylphenol;2,3-dimethyl-e-ttoctylphenol; 2,5-dimethyl-4-tt-octylphenol: 2-ethyl-i-tt-octylphenol; 3-ethyl-4-tt-octylphenol;4-ethyl-2-tt-octylphenol;

phenol; 3-methoxy-4-tt-octylphenol; 4-methoxy- Z-tt-octyl-phonol;2-chloro-5-methoxy-4-tt-oct ylphe'nol;Z-bromo-5-methoxyi-tt-octylphenol; 2-iodo-5-methoxy-e-tt-octyl'phenol;and tt-octyl-aand fi-naphthols, as well as tt-cctyl substitutedhydroxy-benzolc acids (tt-octyl-salicyllc acid) etc.

or an acid or an alkoxy group, such as: methoxy, ethoxy,

The poly-halogenated carbonyl compounds utilized in this inventioncomprise the following compounds: chloral and chloral hydrate(trichloro-acetaldehyde): tri-bromo-acetaldehyde; tri-ido acetaldehyde;u,,a-triohloro e acetone (1.1.l-trichloro-propanone);1.1,1,-tribromo-pro panone; 1.1,1-tri-iodo-propanone; hexa chloroacetone, hexa bromo acetone, hexa iodo acetone;1.1,1.-trichloro-butanone-2; 1,1,1-tribromo-butanone-2;1,1.1-tri-iodo-butanone-2; 1,1,1,-trichloro-3.3-dimethy1-butanone-2;1.1,1-tribromo- 3,3-dimethyl butanone 2; methyl-butanone 2;w,w,w-trichloro-acetophenone; e.w,w-tribromo-acetophenone;w,w,w-triiodo-acetophenone; 1,1,l-trichloro-hexadlone- 2,4:1,1,1,6,8,6-hexa chloro'-hexadione-2,4; trichloro methyl-p-chlorophenylketone; trlchloro methyl -p-bromophenol ketone; trlchloromethylp-iodophenyl ketone; 7,7,y-t1ich10ro acetoacetic acid and itsesters. I r

The most convenient condensing agents to use are hydrogen chloride,sulfuric acid and benzenesulfonic acid, but acidic metal salts, such asboron trifluoride, aluminum chloride, orzinc chloride might also beemployed. These catalyzers might be used with or without an inertsolvent such as glacial acetic acid, propionic acid and others.

"Example 1.-fl,p,B-trichlord-a.-bis (Z-hydrorij-3-methyl-5-tt-octulphenyl) ethane Two-tenths mol (44 grams) or2-methyl-4 -ttoctylphenol (diisobutyl-o-cresol) is melted together with0.1 mol (14.6 grams) of chloral (trichloro acetaldehyde) or chloralhydrate (16.4 grams). In a separate vessel, grams of glacial acetic acidare mixed with grams or concentratcdsulfuric acid. This solution isfirst cooled z-methoxyi-tt-octyl- 1,1,1-tri-iodo-3,3-di-.

externally in ice water and is then slowly added to the phenol-aldehydemixture which has also been cooled externally in a similar manner. Thereaction mixture is well shaken to assure complete mixing and is thenallowed to stand at a temperature of about for several hours. As maximumviscosity is reached the mixture is Poured into ice water, or if it istoo thick, pieces of ice are added to the reaction material. Formation01 heat is avoided throughout the entire condensation process, Finallythe material is broken up, well washed with cold water and then withboiling water, and then separated by filtration, decantation orcentrifuging. It is then allowed to dry in air. At this stage thereaction product is a waxy solid, pure enough for most uses. It may befurther purified by crystallization from suitable organic solvents suchas ethyl alcohol, ethyl acetate, chloroform, benzene, diisobutylene orglacial acetic acid. The melting point is 125 C.

Example 2.-;3,p,fl-trichloro-a,a-bis (Z-hydrOxy-3-methoxy-5-tt-octwlphenyl) ethane Two-tenths moi (47.2 grams) oiZ-methyl-i-ttoctyiphenol (diisobutyl-guaiacol) are dissolved withwarming in 100 cc. of glacial acetic acid. To this solution is added 0.1mol (14.6 grams) of freshly distilled chloral (trichloro acetaldehyde).Dry hydrogen chloride gas is then passed into the mixture untilsaturated. The mixture is then set aside and the saturation with dryhydrogen chloride is repeated every 24 hours for a week. After this timethe reaction mixture is poured into cold water whereby an oil orsemi-solid separates out. The reaction product is then removed from thesupernatant aqueous layer and repeatedly treated with hot distilledwater until free from acetic acid, hydrogen chloride and any unreactedchloral. At this stage the reaction product is pure enough for mostpractical uses. It may be further purified as directed in Example 1. Itsmelting point is 115-l18 C.

Two-tenths mol (41.2 grams) of p-tt-octylphenol (diisobutylphenol) isdissolved with warming in 50 cc. of glaci acetic acid. To this solutionTwo-tenths mol (41.2 grams) of p-tt-octylphenol' (diisobutylphenoD-aremelted and then intimately mixed with 0.1 mol (26.2 grams) of hexachloroacetone. This mixture is then cooled externally in an ice-salt mixture.Under constant stirring and while the temperature of the reactionmixture is keptat zero degree or below,

seventy grams of cold concentrated sulfuric acid is added in smallamounts. After completion of the addition of the sulfuric acid thereaction mixture is set aside for several days. After the mixture hasbecome very thick and almost semi-solid, it is poured into ice water orpieces of ice are added to the condensation mixture. Finally thecondensation product is broken up. washed with cold water and thenrepeatedly washed with boiling water. The product is then separated anddried as described in Example 1. Further purification is effected bycrystallization from suitable organic solvents. M. P. 240 C.

The foregoing examples do not imply that for each particular phenol andpoly-halogenated carbonyl compound a specific catalyzer has to be used,they merely indicate that for the compounds mentioned the given methodappeared to give the better results as indicated by yield and purity ofcondensation products as well as absence or minimum formation ofpolymers. Thus, diisobutylphenol is condensed with chloral in thepresence of dry hydrogen chloride gas, while analogouslydiisobutyi-o-cresol can be condensed with any of the givenpoly-halogenated ketones using cone. sulfuric acid with or without asolvent. Properly blockblocked phenols (J. B.

is added 0.1 mol (16 grams) of a,a,a-tl'l(lhl0r0 acetone. The solutionis then externally cooled in an ice water bath. To this ice cold mixtureis then added approximately 0.3 mol (about 30 grams) of concentratedsulfuric acid. After thor-,

ough mixing, the cold reaction mixture is allowed Niederl et ai., Journ.Am. Chem. 800., vol. 63. p. 1731 (1941)) such as the Z-methyior 2-methoxy-. or 2-chloro-4-tt-octylphenols give the purest condensationproducts as the formation of undesirable polymers is stericallyprevented.

Of the large number of halogenated condensation products possible underthis invention, the following may be considered as typical:

Name of Condensation Product Formula Prepared trom- Dlisohutylphenol andchloral.

Diisohutylphenol and camatrichloro acetone. Diisohutylphsnol and u,u,w-

trichloro acetophouone. Dilsobutylphenoi and hexachioro acetone.Dllsobutyi-ocresol and chloral.

Dllsohutyl-n crcsol and moantrichloro acetone.

Dilsobutyl-o-cresol and (0,03,00-

trichloro ncctonhcnone.

chioro acetone. Dllsobutyl-glmiucol undchioml.

Diisobutyl-o-crcsol and hcxu- Chloro dilsobutylphenoi and chloral.

From the above, it becomes apparent that the i .B.B-trihalo-a,-bis (2hydroxy 8 alkyl-S-ttinvention is susceptible of a great number ofoctyl-phenyl) ethanes.

' modifications and variations withinthe spirit of OSEPH B. NIEDERL. theinvention. Many other products than those specifically named may beproduced in accord- 5 REFERENCES CITED ance with the disclosure hereinand the starting The following references are of record in the materialsfor the reaction may differ considerfile of this patent:

ably. Therefore, theinventlon is to be broadly construed and not *tobelimited except by the V UNITED STATES PATENTS claim appended hereto. 10Number Name Date lclaim: 1,986,423 Arvin Jan. 1, 1935 The insecticidaland bactericidal products 2,329,074 Muller Sept. 7, 1943

